GB1584716A - Carboxylic fused furan derivatives and their use as optical brighteners - Google Patents

Description

PATENT SPECIFICATION ( 11) 1584716

C ( 21) Application No 23660/77 ( 22) Filed 3 June 1977 ( 31) Convention Application No7119/76 ( 1 ( 32) Filed 4 June 1976 in a ( 33) Switzerland (CH) ( 44) Complete Specification published 18 Feb 1981 ( 51) INT CL 3 C 07 D 413/02; D 06 L 3/12 ( 52) Index at acceptance C 2 C 1432 1473 1475 200 213 215 220 226 22 Y 246 253 255 Y 28 X 305 30 Y 364 366 368 36 Y 37 X 61 X 624 628 X 668 672 699 77 Y 794 80 Y AA BC WC ZB ZD ( 54) CARBOCYCLIC FUSED DERIVATIVES AND THEIR USE AS OPTICAL BRIGHTENERS ( 71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of German, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the 5 following statement:-

Benzofuran compounds which are linked by a stilbene bridge to the 3phenyl1,2,4-oxadiazolyl-( 5)-radical have been described in Helv Chim Acta 57, 1370 ( 1974) However, as the fluorescence maxima in these compounds are in the range of from 485 to 490 nm, these compounds are not suitable for use as optical 10 brighteners.

The present invention provides a compound of the general formula wherein:

A represents an aromatic mononuclear or binuclear ring system which is fused 15 with the furan nucleus in the manner indicated, and which may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different, R represents a hydrogen atom, a lower alkyl group, a phenyl group which may be unsubstituted or substituted by one or more non-chromophoric substituents 20 which may be the same or different, or a carboxy group which may be functionally modified; X represents a direct bond or one of the following divalent radicals -CH=CH X 4 Kc II -Nc Y 5 >E 25 and B represents an alkyl, aryl or heteroaryl group, which group may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different.

Suitable non-chromophoric substituents which may be bonded to the aromatic ring system A, or to a phenyl radical represented by R, are preferably lower alkyl, alkenyl and alkoxy groups, alkylene groups, aryl, preferably phenyl groups, carboxy and sulpho groups which may be functionally modified, acyl, acylamino and sulphonyl groups and halogen atoms It is possible for any one of the 5 substituents listed above to be itself substituted.

The expression "lower" used in connection with aliphatic groups should be understood to indicated groups having up to 6, preferably up to 4, carbon atoms.

A functionally modified carboxy group is preferably a carboxy anion associated with a colourless cation, an alkali metal or ammonium ion being 10 preferred; or, especially, a cyano group, a carboxylic acid ester group or a carboxylic acid amide group Carboxylic acid ester groups are preferably those of the general formula -COOR 1, in which R' represents a phenyl group or a lower alkyl group, which groups may be unsubstituted or substituted by, for example, a dialkylamino, trialkylammonium or alkoxy group, preferably wherein each alkyl 15 group is a lower alkyl group A carboxylic acid amide group is preferably one of the general formula -CONR 2 R 3 or -CONHNR 2 R 3, in which each of R 2 and R 3, which may be the same or different, represents a hydrogen atom or a lower alkyl group, which may be unsubstituted or substituted, or R 2 and R 3 together with the nitrogen atom to which they are bonded, represent a hydroaromatic ring 20 A functionally modified sulpho group is preferably a sulpho anion associated with a colourless cation, preferably an alkali metal or ammonium ion, or a derivative in which the SO 2-group is bonded to a hetero atom, for example in a sulphonic acid ester group or in a sulphonamide group A sulphonic acid ester group is especially one of the general formula SO 2 OR 1, in which R' has the above 25 meaning, and a sulphonic acid amine group is especially one of the general formula SO 2 NR 2 R 3, in which R 2 and R 3 have the meanings given above.

An acyl group is especially one of the general formula COR 4, in which R 4 represents an alkyl group, preferably a lower alkyl group, or a phenyl group, which groups may be unsubstituted or substituted 30 A sulphonyl radical is especially one of the general formula SO 2 R 5, in which R 5 represents a lower alkyl or a phenyl group, which groups may be unsubstituted or substituted, a preferred substituent being a lower dialkylamino, trialkylammonium, acylamino or sulpho group.

B may for example represent an alkyl group which is substituted by one or 35 more of the same different substituents selected from halogen atoms, amino, alkylamino, dialkylamino, heterocyclic, phenyl, phenoxy, alkoxy, alkylthio and phenylthio groups, which groups may be unsubstituted or substituted: for example, an alkoxy or alkylthio group may be substituted by one or more of the same or different substituents selected from alkoxy, alkylthio, amino, alkylamino, dialkyl 40 amino, and heterocyclic groups, and a phenyl moiety may be substituted by, for example one or more of the same or different substituents selected from alkyl, preferably lower alkyl, heteroaryl, carboxy and functionally modified carboxy groups and halogen atoms.

B preferably represents one of the following groups: 45 LIST 1 methyl, ethyl, n or i-propyl, n or i-butyl, pentyl,,-chloroethyl, /3dimethylaminoethyl, p-diethylaminoethyl, N-/3-morpholinoethyl, N-ppiperidinoethyl, N-,(N'-methylpiperazino)-ethyl, benzyl, phenoxymethyl, p-phenoxyethyl, pchlorophenoxyethyl, p-ethylthioethyl, p 3-phenylthioethyl, CH 2 CH 2 OCH 3, 50 CH 2 CH 2 OC 2 Hs, CH 2 CH 2 OC 3 H 7, CH 2 CH 2 OC 4 Hg, CH 2 CH 20 CH 13, C 4 H 9 CH 2 CH 2 OCH C 2 Hs CH 2 CH 2 OC 6 H 1,, (CH 2 CH 20)2 CH 3, (CH 2 CH 20)2 C 2 Hs, (CH 2 CH 20)2 C 4 Hg, (CH 2 CH 20)3 C 2 Hs, CH 2 CH 2 OCH 2 CH 2 SC 2 Hs, CH 2 CH 2 OCH 2 CH 2N(CH 3)2, CH 2 CH 2 OCH 2 CH 2-N(C 2 H 5)2 or 55 1.584 716 C 2 C 20 o 2 Chz Cf 2 o O Preferred compounds of the general formula (I) are compounds of the general formula A:,tig _ X,__ o' ( 2) in which each of R' and R 2 ', which may be the same or different, represents a 5 hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a phenyl group which may be unsubstituted or substituted by one or more nonchromophoric substituents which may be the same or different, a carboxy group which may be functionally modified, or R" and R 2 ' together represent a fused benzene nucleus; 10 R' represents a hydrogen atom or a lower alkyl group; X' represents one of the following divalent radicals:

and B' represents an alkyl group having from I to 6 carbon atoms which may be 15 unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different, an alkoxyalkyl group, a phenyl radical which may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different, or one of the groups 0 or O _ r 20 2 O -/2 L 9 or O Oa Of especial interest are the compounds of the general formula R # N ' ( 3) s XL BO.

in which each of RI" and R 2 ", which may be the same or different, represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, or R"' and R'2 " together represent a benzene ring fused in the 4,5-position; 25 X' has the meaning given above; and B" represents an alkyl group having from I to 6 carbon atoms, a (C 1-C 4) alkoxy-alkyl group, a phenyl group, a (C, -C 4) alkyl-phenyl group, a halophenyl group, a (C 1-C 4) alkoxy-carbonylphenyl group or a group of the formula 0, 30 or O The invention also provides a process for the preparation of a compound of the general formula (I), which comprises:

(I) reacting a carboxylic acid chloride of the general formula 1584,716 I r R 4716 A)vx-C/Cg ( 4) wherein A, R and X have the meanings given for the general formula ( 1), with an amide oxime of the general formula B-e NH 2 / ( 5)2 B C N-OH wherein B has the meaning given for the general formula (I), or a salt thereof, preferably in the presence of an acid-binding agent, preferably in an inert solvent, preferably at a temperature in the range of from 20 to 200 C, preferably 160 to 180 C, and preferably using the reactants in a molar ratio of substantially 1:1; or 10 (II) cyclising a compound of the general formula -R N -B f 2-Xow ( 8) A.oc H/2-x o 2 wherein A, B, R and X have the meaning given for the general formula ( 1); and if desired, converting the compound of the general formula ( 1) resulting from process 15 (I) or (II) into another compound of the general formula ( 1).

The conversion of a compound resulting from process (I) or (II) is suitably carried out by conventional methods.

Suitable solvents for the reaction (I) are, for example, ethylene chloride, chlorobenzene, dichlorobenzene, trichlorobenzene, and, especially, dimethyl 20 formamide, N-methylpyrrolidone, dimethylsulphoxide and nitrobenzene Suitable acid-binding agents are, for example, Na 2 CO 3, K 2 CO 3, Ca CO 3 and tertiary amines.

After a reaction time generally of one or two hours, HCI and Hz O are split off to yield directly a compound of the general formula ( 1), which, on cooling the reaction mixture, generally crystallises out in good yield and practically pure 25 The starting materials of the formula ( 4) and ( 5) are known or may be produced in a manner analogous to processes known per se (German Offenlegungsschrift No 2,238,628) Thus a compound of the general formula 4 may be obtained by reacting a compound of the general formula AJ( O ( 6) 30 3 OH wherein A has the meaning given for the general formula ( 1), with a compound of the general formula CICH 2-X-CN wherein 35 X has the meaning given for the general formula ( 1) Subsequently the cyano group is hydrolysed to form a carboxy group and the carboxy group is converted into an acid chloride group The production of a compound of the general formula ( 5) may be effected by reacting a cyano compound of the general formula B-CN 40 wherein B has the meaning given for the general formula ( 1), with hydroxylamine A 1 5 -5 hydrochloride, preferably in ethanol/water at 801 C Subsequently the free base is released by adding soda It is possible to use, for example, the following compounds as carboxylic acid chlorides of the general formula ( 4) in process (I) LIST 2 C#3 f &-coc-e #3 c #SC C# T CO Cep '#9 11 Y li:O CO ce' 11340 C/I-n O e-o ce cells core O wc? 1 #SC i ococe #SC Coce 113 C#5 IISCG 703 coc,,0 #SC C 83 lr COC 14 #3 c o (C 113)3 C.

'ococl Core 1 Y 3 C 1 ,ococl There may be used as amide oxides of the general formula ( 5), for example:

LIST 3 is is 4 _ -1 m N-110 I-111 eI & </ v ^ 12 W-Oly Yh,2 /ISCO 2 C --C % W-0# C#3 c "',VOW c"IVY 2 O O# (, cl-is 1.584316 1,584,716 /N 0 NH 2 00 /NO The compound of the general formula ( 8) may be cyclised by any suitable method, preferably using an alkali metal hydroxide in a polar solvent, for example dimethylformamide, hexamethyl phosphoric acid trisamide, diethylformamide or dimethylacetamide, suitably at a temperature in the range of from 0 to 160 C, or using an alkali melt without a solvent, suitably at a temperature in the range of from to 400 C Preferably the compound of the general formula ( 8) is converted into its anil before cyclisation.

A compound of the general formula ( 8) may be prepared by etherifying an aldehyde of the general formula ( 6) OH wherein A and R have the meanings given for the general formula (I), with a halomethyl compound of the general formula ( 7) wherein X and B have the meanings given for the general formula (I) and Hal represents a halogen atom Preferably the compounds ( 6) and ( 7) are reacted in a molar ratio of substantially 1:1 The following compounds may be used as carbonyl or halomethyl compounds of the general formula ( 6) and ( 7) respectively in the process described under (II) LIST 4 C/g o H CH 1 x ON #3 c CN 101 #i CJ Po J-0 C/ ( 10 'c 3 C / OH 0/ 0 CI O g O O c o Zi S ho CHT'^ -" OH MS C/=o o H CA 3 hi COC= O /1 z C OU CN$ 1/SCO C= O 12 J 10 R I /-3 c_ c H 3 C 0/i'l c N O C/b NO _ HO OVO 101 C/ o H N-F 8 {-7 1584,716 LIST 5 LIST 5 N '-"W CH 3 Br CH 2 o 'f r C 52 > 3;_ O CH xv N< -I T Cd 3 Br CH 2 ov C// N j CH 3 Br CM 2 o C/I 3 /v O N & 3 C-e W 2 -j-CA/o C-k Br r 12, o O O A compound of the general formula (I) resulting from the process of the invention may be converted into another compound of the general formula (I), for example by sulphonation with a sulphonating agent, for example H 2 SO 4, a mixture of H 2 SO 4 and SO 3, or chlorosulphonic acid; the conversion of sulpho or carboxy groups into function modified sulpho or carboxy groups, or the conversion of such functionally modified groups into other such groups or into the free sulpho or carboxy groups; chloromethyl groups may be introduced; methyl groups may be oxidised; the compound may be halogenated, and the halogen atom introduced may be further reacted, for example a chlorine or bromine atom may be replaced by a -C=N group or an amine function.

The compounds of the general formula (I) are generally colourless or slightly yellow and have fluorescence maxima in the range of from 410 to 45 nm Because of this fluorescent property, the compounds of the invention generally have a wide field of application They are chiefly useful for the optical brightening of a wide variety of synthetic, semi-synthetic and natural high molecular weight materials.

High molecular weight organic materials include polymerization, polycondensation and polyaddition products and after-treatment products thereof, for example polymerization products based on olefinically unsaturated monomers including ca,/3-unsaturated carboxylic acids, olefinic hydrocarbons, and halogenated hydrocarbons, for example polyolefins, polyvinyl chloride, polyvinylidene chloride and polyacrylonitrile; the homo polymers and mixed polymers of bifunctional or polyfunctional compounds with condensable groups, for example polyesters, polyamides, maleic resins, polycarbonates and silicone resins; and polyaddition products, for example crosslinked or noncrosslinked polyurethanes and epoxy resins.

Semi-synthetic organic materials include, for example, cellulose esters and ethers, nitrocellulose, regenerated cellulose and plastics based on casein.

Natural materials that may be optically brightened are, for example, protein materials, for example wool, silk and leaiher; cellulose materials, for example cotton, paper, and finely distributed wood pulp; also rubber, guttapercha and balata.

The organic materials to be optically brightened may be in a wide variety of processing states (raw materials, semi-produced products or finished products) and aggregate states, for example in the form of plates, sheets, moulded articles, shavings, granulates, foam plastics, films, foils, lacquers, webs; fibres, for example in the form of endless threads, staple fibres, flocks, yarns, rope goods, twisted yarns, fibres fleeces, felts, cotton wools, textile fabrics composite materials and knitted materials; powders, cements, pastes, waxes, adhesive compositions and knifing fillers.

1,584,716 The optical brighteners of the invention may also be used when organic materials of the above types are combined with inorganic materials in any form.

The compounds of the invention are, however, preferably used for the optical brightening of fibres, textiles and plastics.

Compounds of the invention insoluble in water, which are suitable especially 5 for the optical brightening of polyester and polyamide fibres, cellulose and regenerated cellulose fibres, and cellulose and regenerated cellulose fibres finished with synthetic resins for the purpose of easy care, alone or in admixture with synthetic fibres, may be used dissolved in organic solvents or in aqueous dispersion, advantageously with the aid of dispersing agents Suitable dispersing agents, are, 10 for example, soaps, polyglycol ethers that are derived from fatty alcohols, fatty amines or alkyl phenols, cellulose sulphite waste liquors or condensation products of optically alkylated naphthalenesulphonic acids with formaldehyde.

The compounds of the invention are generally distinguished by the fact that they can be used in the presence of oxidative or reductive bleaching agents, for 15 example hydrogen peroxide, sodium hypochlorite, sodium chlorite or sodium dithionite, without impairing the optical brightening effect The optical brightener may be combined with other finishing agents for the purpose of improving the effect or simplifying the process Such auxiliaries are, for example, retarders, carriers, dispersing agents, plasticiser, oleophobic or hydrophobic compounds, 20 preparative agents, emulsifiers, washing agents and wetting agents.

Particularly good brightening effects are sometimes obtained when the compounds of the invention are combined with other optical brighteners Such combinations are of particular interest when changes in shade of the brightening effect are desired 25 The brightening of fibres with an aqueous or organic brightener liquor is effected either in the exhaust process at a temperature preferably in the range of from 20 to 1500 C or under thermosoling conditions, in which the textile material is brought to a moisture content of approximately 50 to 120 % with the brightener solution or dispersion, by impregnating and squeezing off, or spraying 30 Subsequently the textile material is subjected for approximately 10 to 300 seconds to a heat treatment, preferably by means of dry heat of approximately 120 to approximately 2400 C This thermosoling process can also be combined with other finishing operations, for example, with synthetic resins for example, with synthetic resins for the purpose of easy care The brighteners according to the invention are 35 generally distinguished by a high resistance to the catalysts and additives customary for this, for example magnesium chloride, zinc nitrate or a polyethylene dispersion.

Synthetic detergents may also be added to the benzofurans of the general formula ( 1) These may contain fillers and auxiliaries, for example alkali metal silicates, alkali metal polyphosphates, alkali metal polymetaphosphates, alkali 40 metal borates, alkali metal salts of carboxymethyl cellulose, foam stabilizers, for example alkanolamides of higher fatty acids, complex formers, for example soluble salts of ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, or chemical bleaching agents, for example percarbonates Very good results are also obtained with perborate-containing synthetic detergents in the presence of 45 perborate activators The disinfectants normally used in synthetic detergents generally do not impair the brightening effects of the compounds of the invention.

A compound of the invention may be added to a high molecular weight organic material before or during processing For example, it may be added when producing a film, foil, web or shaped article from a moulding composition, or it 50 may be dissolved in a spinning composition before spinning Suitable compounds may also be added to the lower molecular weight starting materials before the polycondensation or polymerization, as in the case of polyamide-6, polyamide-6,6 or linear polyesters of the polyethyleneglycol terephthalate type.

Compounds of the invention that are substituted by one or preferably two 55 carboxy and/or alkoxycarbonyl groups, may be bonded to linear polyester molecules and synthetic polyamides by an ester or amide bond, if they are added to these materials or, preferably, their starting materials, under suitable conditions.

Brighteners anchored in the substrate in the manner by a chemical bond are distinguished by an extremely good fastness to solvents and sublimation 60 The quantity of the compound of the general formula (I) to be used in accordance with the invention, based on the material to be optically brightened, may vary greatly depending on the field of use and the desired effect It may be determined in a simple preliminary tests and is generally between 0 01 and 2 %.

The following Examples illustrate the invention 65 I 1,584,716 Example I.

23.8 g of p-lbenzofuran-2-yll-benzoic acid, 15 2 ml of thionyl chloride and one drop of dimethylformamide (DMF) were heated in 150 ml of chlorobenzene for 1 5 hours at 80-100 C The reaction mixture was cooled to 0-5 C, the resulting acid chloride was suction-filtered and washed with chlorobenzene and hexane This 5 crude acid chloride ( 22 g, melting point 166-168 C) was heated with 11 6 g of benzamide oxime and 8 6 g of triethylamine in 250 ml of Nmethylpyrrolidone for 2 hours at 160-180 At 0-5 C the resulting crystals were suction-filtered and washed with ethanol 23 1 g of the compound of the formula ( 101) were obtained.

m ( 101) 10 This compound was recrystallised from butanol with the addition of Tonsil (Tonsil is a trade mark).

Yield: 20 6 g Melting point: 205-2060 C Analysis: C 22 H 1402 N 2 ( 338 4) Calculated: C 77 9 H 4 2 N 8 3 15 Found: C 77 4 H 4 1 N 8 5 Absorption: Amax: 340 nm (DMF) E = 4 4 104 The compounds of the general formula ( 102) listed in the following Table were produced in a similar manner.

1,584,716 TABLE 1

0 / ( 102) Melting point Formula Analysis (%) or clarification recrystallised Absorption in DMF Example No B C H N temperature l Cl from X max lnml E 10-CH 3 ' _H 3 CH 3 calc 73 9 44 10 1 found 741 4 4 ' 10 0 calc 78 5 4 6 found 78 6 46 calc 78 5 4:6 found 78 1 4 6 calc 78 5 4:6 found 78 4 4 6 calc 77 3 4 O found 77 1 3 9 7.95 7.8 7.95 8.3 7.95 7.9 6.2 6.1 197 198 178 179 164 165 232 233 302 304 toluene Bu OH Bu OH toluene DMF 336 339 339 338 346 5.43 4:37 4.29 4:4 8.05 ( 102 a) ( 102 b) ( 102 c) ( 102 d) ( 102 e) TABLE 1 (continued) Melting point Formula Analysis (%) or clarification recrystallised Absorption in DMF Example No B C H N temperature l Cl from k max tnml E 104 7 ( 102 f) _ calc 81 8 4 6 6 4 360 DMF 372 6 08 found 81 9 4:6 6 2 8 ( 102 g) C 02 C 3 calc 72 7 4 1 7 1 225 tol 341 4 76 found 72 8 41 7 0 9 ( 102 h) calc 80 9 4 0 5 6 292 294 DMF 354 8 16 0- found 812 4 0 5 4 362 ( 102 i) \h Il calc 76 2 3 7 7 4 230 232 DMF 341 4 76 found 76 1 3 8 7 4 liquid-crystalline behaviour Oc 12 1,584,716 12 Example 11.

In a manner analogous to that described in Example I the compound of the formula ( 103) ( 103) 0 j IN was produced from naphthofuran-2-carboxylic acid chloride of the formula 5 Cocoat with benzamide oxime.

Yield: 51 % Melting point: 183-184 C (toluene) Analysis: C 20 H,2 N 202 ( 312 31) Calculated: C 77 1 H 3 9 N 9 0 10 Found: C 77 1 H 4 0 N 9 0 Absorption: Amax = 351 lnml (DMF) Example 12.

In a manner analogous to that described in Example I the compound of the formula ( 104) was produced from naphthfuran-2-yl-phenyl-4 '-carboxylic acid 15 chloride with benzamide oxime 0 No/( 104) Yield: 84 % Melting point: 265-266 5 (DMF) Analysis: C 2,H 16,N 202 ( 388 4) Calculated: C 80 3 H 4 15 N 7 2 20 Found: C 80 6 H 4 3 N 7 3 Absorption: Amax = 365 nm (DMF) E = 4 4 104 The compounds of the formula ( 104 a-104 g) listed in the following Table 2 were produced in a corresponding manner.

TABLE 2 o& o O -1 ' ( O o IOM ( 104 a-104 g) Melting point or Analysis clarification recrystallised Absorption in DMF Example Formula B' C H N temp l Cl from Xmax lnml c 10 4 calc.

found 77.2 4 3 77.5 4 3 8.6 8.4 ' calc 80 6 4 '5 7 0 found 80 7 4 6 6 9 calc 80 6 4:5 7 0 found 80 6 4:5 7 3 calc.

found 80.6 4:5 80.6 4:5 7.0 6.8 calc 75 4 4 05 6 3 found 75 7 4 1 6 1 calc.

found 81.0 3 98 80.9 3 9 5.6 5.6 -C 13 p.c _ 3 CH { CH 3 CH 3 -(X+ 02 e:-3 ( 104 a) ( 104 'b) ( 104 'c) ( 104 d) ( 104 e) ( 104 f) 221 223 219 220 220 221 254 255 261 (clear) 224 310 (clear) 279 280 368 (clear) ZA tol DMF DMF DMF BME DMF 362 363 363 363 365 363 4.15 4:46 4.50 4.49 4 40 5.82 TABLE 2 (continued) Melting point or Analysis clarification recrystallised Absorption in DMF Example Formula B' C H N temp L Cl from Amax Inml E 104 19 ( 104 g),0 } calc 82 2 4 0 5 1 303 305 DMF 373 8 75 0 k| found 82 5 4 O 5 0 > 360 00 -J cn Liquid crystalline behaviour.

BME = benzoic acid methyl ester.

In a manner analogous to that described in Example 1 the compounds of the formula ( 105 a) to ( 105 Sf) listed in Table 3 were prepared TABLE 3

8 ' O ' O BV R 2 Analysis c HB N ( 105 a) ( 105 f) Melting point or clarification temp lOCI recrystallised from.

Absorption in DMF Armax Inmj E l O calc.

found 5 4,6 9 16 70.5 4 6 9 0 calc 75 4 5 7 8 8 found 75 7 5 8 8 6 calc 78 6 4 9 776 found 78 2 4 9 7 6 calc 796 4 6 5 8 found 79 6 4 7 5 8 calc 78 5 4 6 7 95 found 78 5 4 6 7 9 calc 75 4 4 4 7 6 found 75 7 45 7 2 liquid-crystalline behaviour.

Examp lc Formula No 1,9 i 3 CH 3 ( 105 a) ( 105 b) ( 105 c) ( 105 d) ( 105 e) ( 105 f) H 3 C Cl 3 CH 3 Hic CH 3 CH 3 H 3 C H 3 CO> 189, 206 147 149,5 168 170 223 192 194 182 184 264 tol Et O l-1 to 11 DMF tol DMF 344, 346 349.

348 343 348 L^ 0 " 3.73 3.21 3.91 7.08 4.40 4.04 I II I 584716 ID l,- - Example 26.

From the carboxylic acid of the formula ( 106), ( 106) which after conversion into the corresponding acid chloride was reacted in 5 accordance with Example I with benzamide oxime, the compound of the formula ( 107) was produced CH=C Hg L S < o"N( 107) Yield: 67 % Melting point: 215 C (toluene) Analysis: C 24 H 15 N 202 ( 364 4) Calculated: C 79 3 H 4 4 N 7 7 Found: C 79 6 H 4 7 N 7 7 Absorption: Amax = 365 nm (DMF) E = 4 7 104 Example 27.

The benzamide oxime in Example 26 was replaced by the equivalent amount 15 of acetamide oxime and the compound of the formula ( 108) was thence obtained.

0 108) Yield: 77 % Melting point: 184-186 C Analysis: Cg H,4 N 2 N 202 ( 302 3) Calculated: C 75 5 H 4 67 N 9 3 20 Found: C 75 9 H 4 6 N 9 1 Absorption: Amax = 362 nm (DMF) E = 4 83 104 Example 28.

A fabric of texturised polyester was padded with a dispersion containing 0 75 g/l of the brightener of the formula ( 104) and squeezed off on a foulard to a residual 25 moisture content of 85 % It was then dried and subjected to a thermosol process for seconds at 170 C on a tenter The material treated in this manner exhibited a considerable increase in brightness Similar results were obtained with the same amount of compound ( 107).

Example 29 30

A fabric of polyester-staple fibre was impregnated with a dispersion containing 0.75 g/l each of the compounds ( 104) and ( 107) or ( 108), or alternatively 1 5 g/l of the compound of the formula ( 104 a) The fabric was squeezed off to a residual moisture content of 69 % By drying and thermosoling at 190 C for 30 seconds, a material was obtained which exhibited a significant increase in brightness when 35 compared with untreated material.

Equally good results were obtained with the compounds ( 104 a) and ( 107) in the exhaust process under high temperature conditions on polyester-staple fibres at C and on cellulose triacetate at 98 C The liquor contained 0 15 % each of the compounds ( 104 a) and ( 107) and the liquor ratio was 1:20 40 Example 30.

A polyamide fabric was treated for I hour on a high temperature apparatus at 17184161 C and a liquor ratio of 1:20 with a liquor containing 0 15 % by weight of compound ( 104) or ( 1040 f) A considerable increase in the brightness was noted.

Example 31.

A polyester fabric was treated for I hour at 98 C and a liquor ratio of 1:20 with a liquor containing, in addition to 0 15 % by weight of compound ( 108), I g/l of a 5 carrier based on o-phenylphenol After cooling, washing and drying, a considerable increase in the brightness of the material was noticed.

Example 32.

mg of compound ( 108) was dispersed in 25 g of dioctylphthalate 75 g of polyvinyl chloride, which contained 2 % of titanium dioxide and 0 2 % of a wax, was 10 stirred into this paste In addition, 1 5 g of a stabiliser were added A rolled sheet was produced from this mixture on a cylinder mill in 10 minutes at 160 C This sheet exhibited a significantly higher degree of brightness than a sheet of the same composition but without brighteners of the invention.

Claims (1)

1. WHAT WE CLAIM IS: 15

   l A compound of the general formula ( 1) wherein:

   A represents an aromatic mononuclear or binuclear ring system which is fused wth the furan nucleus in the manner indicated, and which may be unsubstituted or 20 substituted by one or more non-chromophoric substituents which may be the same or different, R representsa hydrogen atom, a lower alkyl group, a phenyl group which may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different, or a carboxy group which may be functionally 25 modified; X represents a direct bond or one of the following divalent radicals -CH=CH 3 and B represents an alkyl, aryl or heteroaryl group, wherein each group may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different.

   2 A compound as claimed in claim 1, wherein the ring system A is substituted 35 by one or more of the same or different substituents selected from lower alkyl, lower alkoxy, lower alkenyl, alkylene, aryl, carboxy, sulpho, functionally modified carboxy, functionally modified sulpho, acyl, acylamino and sulphonyl groups and halogen atoms.

   3 A compound as claimed in either claim 1 or claim 2, wherein B represents 40 an alkyl group which is substituted by one or more of the same or different substituents selected from halogen atoms, amino, alkylamino, dialkylamino, heterocyclic, phenyl, phenoxy, alkoxy, alkylthio and phenylthio groups, all of which groups may be unsubstituted or substituted by one or more nonchromophoric substituents which may be the same or different 45 1,584,7166 4 A compound as claimed in claim 3, wherein any alkoxy or alkylthio group which is a substituent of an alkyl group B is substituted by one or more of the same or different substituents selected from alkoxy, alkylthio, amino, alkylamino, dialkylamino and heterocyclic groups, and any phenyl moiety present in a substituent of an alkyl group B is substituted by one or more of the same or 5 different substituents selected from alkyl, heteroaryl, carboxy and functionally modified carboxy groups and halogen atoms.

   A compound as claimed in any one of claims I to 4, wherein the compound contains as a substituent a carboxy anion associated with a colourless cation, a cyano group, a carboxylic acid ester group or a carboxylic acid amide group 10 6 A compound as claimed in any one of claims I to 5, wherein the compound contains as a substituent a sulpho anion associated with a colourless cation, a sulphonic acid ester group or a sulphonamide group.

   7 A compound as claimed in any one of claims I to 6, wherein any acyl group is a group of the general formula -COR 4, wherein R 4 represents an alkyl or a phenyl group, wherein each group may be unsubstituted or substituted.

   8 A compound as claimed in any one of claims I to 7, wherein any sulphonyl group is a group of the general formula -SO 2 R 5, wherein Rs represents a lower alkyl or a phenyl group, wherein each group may be unsubstituted or substituted.

   9 A compound as claimed in any one of claims I to 8, wherein B represents any one of the groups given in List I herein.

   A compound as claimed in claim 1, which has the general formula R'f / B 117 f 11 ( ( 2) X Rit N B o XY -o in which each of R"' and R 2 ', which may be the same or different, represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a 25 phenyl group which may be unsubstituted or substituted by one or more nonchromophoric substituents which may be the same or different, a carboxy group which may be functionally modified, or R' and R 2 ' together represents a fused benzene nucleus; R' represents a hydrogen atom or a lower alkyl group; 30 X' represents one of the following divalent radicals:

   and B' represents an alkyl group having from I to 6 carbon atoms which may be unsubstituted or substituted by one or more non-chromophoric substituents which 35 may be the same or different, an alkoxyalkyl group, a phenyl radical which may be unsubstituted or substituted by one or more non-chromophoric substituents which may be the same or different or one of the groups 0 --uoj or O 11 A compound as claimed in claim 10, which has the general formula 10 ( 3) N 1,584,716 in which each of RI" and R 2 ", which may be the same or different, represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, or RI" and R 2 " together represent a benzene ring fused in the 4,5-position; X' has the meaning given in claim 10; and B" represents an alkyl group having from I to 6 carbon atoms, a (C, to 5 C 4)alkoxy-alkyl group, a phenyl group, a (C, to C 4)alkyl-phenyl group, a halophenyl group, a (C,-C 4)alkoxy-carbonylphenyl group or a group of the formula -Q or O 12 A compound as claimed in claim I and described in any one of the Examples herein 10 13 A process for the preparation of a compound as claimed in claim 1, which comprises:

   (I) reacting a carboxylic acid chloride of the general formula A)I 7 J Cxc a/ ( 4) -wherein 15 A, R and X have the meanings given in claim 1, with an amide oxime of the general formula NH 2 B-C ( 5) B-C N-OH wherein B has the meaning given in claim 1, or a salt thereof; or 20 (II) cyclising a compound of the general formula )o A CIN ( 8) wherein A, B, R and X have the meanings given in claim 1; and if desired, converting the compound of the general formula ( 1) resulting from either process (I) or 25 process (II) into another compound of the general formula ( 1).

   14 A process asclaimed in claim 13, wherein process (I) is carried out in the presence of an acid binding agent at a temperature in the range of from 20 to C.

   15 A process as claimed in either claim 13 or claim 14, wherein, in process (I), 30 the molar ratio of the reactants is substantially 1:1.

   16 A process as claimed in any one of claims 13 to 15, wherein the compound of the general formula ( 4) is any one of those given in list 2 herein.

   17 A process as claimed in one of claims 13 to 16, wherein the compound of the general formula ( 5) is any one of those given in list 3 herein 35 18 A process as claimed in claim 13, wherein in process (II) the compound of the general formula ( 8) is obtained by reacting a compound of the general formula CO ( 6) o H 1,584,716 wherein A and R have the meanings given in claim 1, with a compound of the general formula B 11 Ya 1 CJ/2-X-0 z ( 7) wherein 5 B and X have the meanings given in claim I and Hal represents a halogen atom.

   19 A process as claimed in claim 18, wherein the cyclisation is performed either with an alkali metal hydroxide in a polar solvent or in an alkali melt.

   20 A process as claimed in either claim 18 or claim 19, wherein the molar ratio 10 of the reactant ( 6) and ( 7) is substantially 1:1.

   21 A process as claimed in either claim 18 to 20, wherein the compound of the general formula ( 6) is any one of those given in list 4 herein.

   22 A process as claimed in either claim 18 to 21, wherein the compound of the general formula ( 7) is any one of those given in list 5 herein 15 23 A process as claimed in claim 13, carried out substantially as described in any one of Example l to 27 herein.

   24 A compound as claimed in claim l, whenever prepared by a process as claimed in any one of claims 13 to 23.

   25 A method of optically brightening a material, which comprises treating the 20 material at any suitable stage in the processing of the material with a compound as claimed in any one of claims I to 12 and 24.

   26 A method as claimed in claim 25, wherein the material to be optically brightened is a synthetic, semi-synthetic or natural organic polymer.

   27 A method as claimed in claim 26, wherein the material to be optically 25 brightened is a fibre, a textile material or a plastics material.

   28 A method as claimed in either claim 26 or claim 27, wherein the material to be optically brightened also comprises one or more inorganic components.

   29 A method as claimed in claim 25, substantially as described in any one of Examples 28 to 32 herein 30 ABEL & IMRAY, Chartered Patent Agents, Northumberland House, 303-306 High Holborn, London WC 1 V 7 LH.

   Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981.

   Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

   1,584,716